N-pentahalophenyl-amino ammonium salts



United States Patent 01 Rice Int. Cl. C07c 87730,-A01n 9/20 US. Cl.260567.6 9 Claims ABSTRACT OF THE DISCLOSURE N-pentahalophenyl-aminoammonium salt having the formula in which A is lower alkylene, R ishydrogen or alkyl, at most one R group is arylmethyl, optionallysubstituted with halo, nitro, alkoxy, alkyl and/or methylene dioxy, atleast two R groups are aliphatic, optionally halosubstituted, X ischloro and/or bromo, and Z is a saltforming anion, e.g. halo-anion,which possesses bactericidal activity and which may be produced byconventional methods.

The present invention relates to particular new N-pentahalo-phenyl-aminoammonium salts which may be used as active compounds for combatingphytopathogenic bacteria, to their bactericidal compositions withdispersible carrier vehicles, and to methods for the production and usethereof.

Organic synthetic compounds for combating phytopathogenic bacteria havenot yet been used.

It is known, however, that cupric oxychloride can be used in plantprotection for combating phytopathogenic bacteria. In spite of its highfungicidal activity, nevertheless, this active compound has only aslight bactericidal effect. As no other bactericides are available forcombating phytopathogenic bacteria, cupric oxychloride has a certainimportance in practice, in spite of its relatively poor effect.

It is an object of the present invention to provide particular newN-pentahalophenyl-amino ammonium salts which possess valuablephytopathogenic bactericidal properties; to provide active compositionsin the form of mixtures of such compounds with liquid and soliddispersible carrier vehicles; to provide processes for producing suchcompounds; and to provide methods of using such compounds in a new way,especially for combating phytopathogenic bacteria.

Other and further objects of the present invention will become apparentfrom a study of the within specification and accompanying examples.

It has now been found in accordance with the present invention that theparticular new N-pentahalophenylamino ammonium salts having the formulaX X t l I R! I!!! R X X (I) in which A is lower alkylene having at least2 carbon 3,518,308 Patented June 30, 1970 atoms, R is selected from thegroup consisting of hydrogen and alkyl having 1-4 carbon atoms, each R"respectively is selected from the group consisting of arylmethyl having6-10 carbon atoms in the aryl moiety; such arylmethyl which issubstituted with at least one member selected from the group consistingof halo, nitro, lower alkoxy, alkyl having 1l2 carbon atoms, methylenedioxy, and mixtures thereof; lower aliphatic; and halo lower aliphatic;with the proviso that at most one R is such an aryl methl, each Xrespectively is selected from the group consisting of chloro and bromo,and Z is a corresponding salt forming anion, have strong bactericidalproperties against phytopathogenic bacteria.

More particularly, the compounds of the present invention surprisinglyhave a higher bactericidal activity against phytopathogenic bacteriathan the cupric oxychloride known in the art.

The particular new pentahalo-phenyl-amino ammonium salts of the presentinvention may be obtained by the process which comprises reactingN-pentahalo-phenylamines of the formula in which A, R, R" and X have thesame meaning as defined above, with alkylating agents containing aradical R as the alkylating radical, optionally in the presence ofdiluents. When N'-pentachlorophenyl N ,N ,Ntrimethyl-hexamethylene-diamine and 2,4-diisopropyl-benzyl chloride areused as starting materials, the course of the reaction can beillustrated by the following equation:

Cl CH(CH3)2 (III) Individual examples of N-pentahalo-phenyl-diamineswhich can be reacted in accordance with the present invention are thefollowing:

N -pentachlorophenyl-N ,N -dimethyl-ethylamine-diamine N-pentachlorophenyl-N -allyl-N rnethyl-ethylenediamine N-pentachlorophenyl-N ,N ,N -trimethyltrimethylene-diamine N-pentachlorophenyl-N ,N -diethyl-trimethylene-diamine N-pentachlorophenyl-N ,N LN -trimethyI- tetramethylene-diamine N-pentachlorophenyl-N ,N -dimethylhexamethylene-diamine N-pentachlorophenyl-N ,N ,N -trimethylhexamethylene-diamine N-pentachlorophenyl-N ,N -dimethyl-N -benzylhexamethylene-diamine N-pentachl0rophenyl-N ,N -diallylhexamethylene-diamine N-pentabromophenyl-N LN -dimethyI- hexamethylene-diamine.

The partially alkylated N -pentahalophenyl-diamines used as startingmaterials have not yet been disclosed but they can be obtained byvarious methods.

For example, they can be prepared by methylating appropriateN-pentahalo-phenyl-diamines with a mixture of formic acid andformaldehyde.

They can also be obtained by reacting N ,N -disubstituted or N ,N ,N-tri-substituted alkylene-diamines with hexachlorobenzene by knownmethods (cf. U.S. Pat. 2,829,164).

To prepare the instant N-pentahalo-phenylamino ammonium salts from suchN -pentachlorophenyl-diamines, all conventional alkylating agents whichcontain an alkylating radical R" as defined above can be used. Thefollowing is a list of typical individual alkylating agents of the typewhich may be used:

allyl chloride ethyl bromide benzyl iodide butyl iodide 3-chloroallylchloride 2,5-dimethyl-benzyl chloride 4-isododecyl-benzyl chloridemethane-phosphonic acid dipropyl ester methyl chloride 3-nitrobenzylchloride propargyl chloride toluene-sulfonic acid methyl ester trimethylphosphate 1-chloromethyl-naphthalene diethyl sulfate2,5-diisopropyl-benzyl chloride 3,4-dichloro-benzyl chloride2,4-dimethyl-benzyl chloride Suitable diluents for the instantalkylation are alcohols, such as butanol; nitriles, such asacetonitrile; ethers such as dioxan and dibutyl ether; and aromatic andaliphatic hydrocarbons, such as benzene, xylene, cyclohexane andmethyl-cyclohexane. The instant N-pentahalophenylamino ammonium saltsare usually insoluble in aliphatic and cycloaliphatic hydrocarbons andcan therefore easily be separated.

To carry out the process according to the present invention, 1 mol ofthe N-pentahalo-diamine is reacted with about 1 to 3 mols, preferably0.95 to 1.1 mols, of the alkylating agent. The reaction temperatures maybe varied within a fairly wide range. In general, the operation iscarried out substantially between about and 130 C., preferably between70 and 110 C. In special cases, for example, when reacting readilyboiling alkylating agents, such as methyl chloride, allyl chloride,propargyl chloride, etc., it may be advantageous to carry out thereaction under pressure. The range of pressure is then determined by thepartial pressure of the alkylating agent.

Moisture must be strictly excluded in order to avoid difficulties inworking up the reaction products since the majority of the compounds areextremely hygroscopic.

Indeed, the particular active compounds according to the presentinvention have a strong bactericidal activity against phytopathogenicbacteria, and advantageously because of their low toxicity towardswarm-blooded animals and their low phytotoxicity they can be used withextremely good results in plant protection against bacterial diseases.

Bactericidal agents are used in plant protection chiefly against speciesof Xanthomonas, Pseudomonas and Erwinia.

The active compounds according to the present invention have provedespecially satisfactory for combating Xanthomolzas malvacearm in cottonand Pseudomonas vesicatoria in tomatoes.

Among the particular compounds of the present invention, the followingare representative:

4 (III) N -[6 (N-pentachlorophenyl-N'-methyl-amino) hexyl] N JNdirnethyl N (2',4-diisopropylbenzyl) ammonium chloride having theformula 01 Cl CH(CI-Ia)2 CH CH3 (IV) N -[2'-(N' pentachlorophenyl-amino)ethyl]-'N N -dimethyl-N -benzyl ammonium chloride having the formula (V)N -[6-(N'-pentachlorophenyl N methyl-amino) hexyl]-N ,N -dimethyl-N -(4'chlorobenzyDammonium chloride having the formula l CH3 CH (VI) N -[6-(N'pentachlorophenyl-N'-methyl-amino) hexyl] N LN dimethyl-N-(4'-nitrobenzyl)ammonium chloride having the formula (VII) N 6-(N'-pentachlorophenyl-N'-methyl-amin0) hexyl] NEN dimethyl-N-(3-nitrobenzyl)ammonium chloride having the formula hexyl]N ,N ,N-trimethylammonium iodide having the formula (IX) ,N -[2-(N'pentachlorophenyl-amino)ethyl]-N N -dlmethyl-N -allyl ammonium chloridehaving the formula (M.P. 181 C) (X) N -[2-(N-pentachlorophenyl-amino)ethyl] -N ,N d1n}ethyl-N -propargyl ammoniumchloride having the formu a or I H on,

(XI) N -[6-(N-pentachloropheny1-N-methyl amino) hexyl] N ,N dimethyl-N-(3,4'-dichlorobenzyl)ammonium chloride having the formula (XII) N [6-(N'-pentachlorophenyl-N'-methyl-amino hexyl]-N N -dimethyl N (2',5'dimethylbenzyDammonium chloride having the formula C1 C1 CH3 I OHa CH3'hexyl] -N ,N -dimethyl-N (2,4' dimethylbenzyl ammonium chloride havingthe formula (XIV) An isomer mixture of N-[6-(N'-pentachlorophenyl-N-rnethylamino) hexyl] N ,N dimethyl-N(2,3-dimethylbenzyl)ammonium chloride and N -[6- (Npentachlorophenyl-N'-methyl-amino)hexyl]-N ,N dimethyl-N -(3Adimethylbenzyl)ammonium chloride having the formula C1 C1 CH3 CH3 3 I im lt cm@ cm $1 or CH3 (XV) N [6 (N'pentachlorophenyl-N'-methylamino)hexyl] N ZN dimethyl-Nl-naphthy1methyl) ammonium chloride having the formula C1 l CH CH (XVI)N [6 N pentachlorophenyl-N-methylamino)hexyl N ,N dimethyl-N-(4'-dodecylbenzyl) ammonium chloride having the formula (XVII) N-[6-(N-pentachlorophenyl amino)hexyl]- N ,N -dially-N -methyl-ammoniummethyl sulfate having the formula 1 1 Hz-CH=CH2 C1 C1 (XVIII) N-[2-(N'-pentachlorophenyl amino)ethyl]- N ,N -dimethyl N (2',5'dimethylbenZyDarnmoniurn chloride having the formula or or CH3 I l CH3 6(XIX) N [4 (N' pentachlorophenyl-N-methylamino) butyl]N ,N dimethyl-N-(2,5'-dimethylbenzyl)ammonium chloride having the formula C1 CH3 l CH3CH (M.P. 183 C) (XX) N [6 (N pentachlorophenyl -N-methylamino)hexyl]-N,N -dimethyl N (3-chloroallyl)ammonium chloride having the formula (XXI)N -[6-(N'-pentabromophenyl amino)hexyl]- N ,N dimethy1-N'(3-chlorallyl)arnmonium chloride having the formula (XXII) N [6 (Npentachlorophenyl-N-methylamino)hexyl]-N -rnethy1-N -(3-chloroally1) Nbenzyl ammonium chloride having the formula I CH3 CH (31 Cl CH2CH=CHCI(XXIV) N -[6-(N-pentachlorophenyl N methylamino)hexyl] N QN dimethyl-N-(4'-ethoxybenzy1) ammonium chloride having the formula c1 or 1 CH3 CH3l l oFQr CHm-I Lore-@ccnt; c1-

(XXV) N -[6-(N'-pentachlorophenyl N methylamino)hexyl] N ,N dimethyl-N-(2,3'-dibromoallyl) ammonium chloride having the formula (XXVI) N -[6(N'pentachlorophenyl N-ethyl-ami- The active compounds according to theinstant invention can be utilized, if desired, in the form of the usualformations or compositions with dispersible carrier vehicles, such assolutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granulates, etc. Theseare prepared in known manner, for instance by extending the activeagents with dispersible liquid diluent cariers and/ or dispersible solidcarriers optionally with the use of carrier vehicle assistants, c.g.,surface-active agents, including emulsifying agents and/or dispersingagents, whereby, for example, in the case where water is used asdiluent, organic solvents may be added as auxiliary solvents (cf.Agricultural Chemicals. March 1960, pages 35-38). The following may bechiefly considered for use as carrier vehicles for this purpose:dispersible liquid diluent carriers, such as aromatic hydrocarbons (forinstance, benzene, toluene, xylene, etc.), halogenated, especiallychlorinated, aromatic hydrocarbons (for instance, chlorobenzenes),paratfins (for instance, petroleum fractions), chlorinated aliphatichydrocarbons (for instance, methylene chloride, etc.), alcohols (forinstance, methanol, ethanol, propanol, butanol, etc), amines (forinstance, ethanolamine, etc.), amides (for instance, dimethyl formamide,etc.), sulfoxides (for instance, dimethyl sulfoxide, etc.), ketones (forinstance, acetone, etc.), and water; as well as dispersible finelydivided solid carriers, such as ground natural minerals (for instance,kaolins, alumina, slica, chalk, i.e., calcium carbonate, talc,kieselguhr, etc.) and ground synthetic minerals (for instance, highlydispersed silicic acid, silicates, e.g., alkali silicates, etc.);whereas the following may be chiefly considered for use as carriervehicle assistants, e.g., surfaceactive agents, for this purpose:emulsifying agents, such as non-ionic emulsifying agents (for instance,polyethylene oxide esters of fatty acids, polyethylene oxide ethers offatty alcohols, and espectially alkyl aryl-polyglycol ethers, etc.); anddispersing agents, such as lignin, methyl cellulose, etc.

As will be appreciated by the artisan, the active compounds according tothe instant invention may be present in such formulations orcompositions in the form of mixtures with one another and with otherknown active substances, if desired.

The substances according to the invention may be employed by themselvesas the artisan will appreciate, in the form of their compositions withsolid or liquid dispersible carrier vehicles or other known compatibleactive agents, or in the form of particular dosage preparations forspecific application made therefrom, such as solutions, emulsions,suspensions, powders, pastes, and granulates which are thus ready foruse.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.l95% by weight, andpreferably 05-90% by weight of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.005 and 0.2% by weight of the mixture.Thus, the present invention contemplates overall compositions whichcomprise mixtures of a dispersible carrier vehicle, such as (1) a.dispersible carrier solid, or (2) a dispersible carrier liquidpreferably including a carrier vehicle assistant, e.g., surface-activeagent, such as an emulsifying agent and/or a dispersing agent, and anamount of active compound which is effective for the purpose in questionand which is generally between about 0.005 and by weight of the mixture.

Furthermore, the present invention contemplates methods of combatingphytopathogenic bacteria which comprise applying to at least one of (a)such bacteria and (b) their habitat, a bacteriacidally, especiallyphytopothogenically bactericidally, elfective amount of the particularactive compound of the invention alone or together with a carriervehicle, as noted above. The instant formulations or compositions areapplied in the usual manner, for example, by spraying atomizing,vaporizing, scattering, dusting, watering, sprinkling, fumigating, andthe like. It will be realized in accordance with the present inventionthat the instant compounds may be used effectively not only forcombating bacteria on leaves and other parts of plants above-ground butalso for seed dressing.

In this regard, when used for treating parts of the plants above-ground,the concentration of the active compound may vary within a fairly widerange. In general, the actual application is carried out withconcentrations between about 0.2 and 0.005 percent by weight asaforesaid, although it will be appreciated that in special cases it ispossible to go above or below this range.

On the other hand, when the active compound is used as seed dressing, itcan be contained in the dressing in an amount of about 5l00%, preferably10-80%, of the dresing. The seed dressings may be used in amounts ofsubstantially between about l-SO g. per kg. seed, preferably 2-15 g. perkg. seed, with the active compound being present in the range ofsubstantially between about 0.05 and 50 g. per kg. seed.

The following example is given for the purpose of illustrating, withoutlimitating, the usefulness of the particular compounds according to thepresent invention:

EXAMPLE 1 Bacteria test/Xanthomonas malvacearum Solvent: 0.9 part byweight acetone Dispersing agent: 0.1 part by weight nonylphenolpolyglycol ether Aqueous suspension of bacteria: 99 parts by weight Theamount of active compound required for the desired concentration of suchactive compound is mixed with the stated amounts of the solvent anddispersing agent and the resulting concentrate is diluted with thestated amount of aqueous suspension of the bacteria.

To prepare the suspension of bacteria, 60 sq. cm. of cotton leavescompletely infested with Xanthomonas malvacearum are mortared, suspendedin one liter water and filtered through gauze.

On each of the first two completely developed leaves of 2 cottonseedlings, three areas of 4 sq. cm. each are infiltrated with a sharpwater jet.

The suspension is sprayed 15 minutes after its preparation onto thetotal of 12 water infiltrated leaf areas.

Seven days after the treatment with the suspension, the infestation ofthe leaf areas is determined as a percentage of the infestation ofinoculated leaf areas of control plants, which have not been treatedwith the active compound: 0% means that no infestation occurred, whereas100% means that the infestation is exactly the same as that of thecontrol plants.

The active compounds, their concentrations and the results obtained canbe seen from the following Table 1:

TABLE 1.BACTERIA TEXT/XANTHOMONAS MALVACEARUM Infestation as percent ofinfestation of untreated control at a concentra- X (Invention) XI(Invention) XII (Invention) XIII (Invention) XIV (Invention)- XV(Invention) III (Invention) XVI (Invention) XXIV (Invention) XXV(Invention)... XXVI (Invention) cccooowbawoomiooooouzooooh-wcn Thepreparation of some of the particular active compounds according to theinvention is described in greater detail by way of illustration and notlimitation, in the following examples:

EXAMPLE 2 Preparation of compound XXII 121 g. N -pentachlorophenyl-N ,N-dimethyl-N -benzyl-hexamethylene-diamine (0.251 mol) and 56 g.cis,trans- 1,3-dichloropropene (0.505 mol) are mixed and kept at 80 for18 hours. The viscous mass crystallizes after the addition of 200 ml.light petrol. After 2 hours, the crystals are separated and washed with300 ml. light petrol. After drying at 70 C., the yield of N -[6-(N-pentachlr0- phenyl N methylamino)hexyl] N -methyl-N -benzyl- N-(3-chloroallyl)ammonium chloride amounts to 144.2 g. (97% of theory,referred to the diamine used). The ammonium salt can be recrystallizedfrom a little toluene. Nitrogen: found 4.91%, calculated 4.72%;chlorine: found 42.0%, calculated 41.96%.

The required starting material is prepared as follows:

165.5 g. N -benzyl-N -pentachlorophenyl-hexamethylene-diamine (0.364mol) are added dropwise in the course of 9 minutes to a mixture, heatedto 80 C., of 85.5 g. 98% formic acid (1.82 mol) and 69 g. of aformaldehyde solution (0.8 mol). The reaction mixture is then kept at 88C. for 4 hours. After working up, 165.5 g. crude N benzyl N ,N-dimethyl-N -pentachlorophenylhexamethylene-diamine are obtained.

EXAMPLE 3 Preparation of active compound VIII 34.1 g. methyl iodide(0.24 mol) are added dropwise in the course of 10 minutes to a solutionof 98 g. N pentachlorophenyl N ,N ,N -trimethyl-hexamethylene-diamine(0.242 mol) in 500 ml. cyclohexane, which is kept at 50 C. The reactionmixture is kept at 50 C. for a further 8 hours, the crystals formed areseparated, washed with cyclohexane and recrystallized from water orchlorobenzene. The yield of N [6-(N -pentachlorophenyl-N methylamino)hexyl] N ,N ,N trimethyl ammonium iodide of M.P. 210 C. amounts to128 g. (96.5% of theory, referred to the diamine used). Carbon: found34.97%, calculated 35.03%; nitrogen: found 4.89%, calculated 5.11%.

10 EXAMPLE 4 Preparation of active compound XIX 270 g. N-pentachlorophenyl-N ,N ,N -trimethyl tetramethylene-diamine (0.713mol), 111 g. 2,5-dimethylbenzyl chloride (0.718 mol) and 100 ml.methyl-cyclohexane are mixed and kept at 82 C. for 40 hours. During thereaction time, the mixture is diluted with a further 600 ml.methyl-cyclohexane. The crystals which formed are separated at roomtemperature, washed twice with 200 ml. methyl-cyclohexane, once with 300ml. acetone and dried in a vacuum at 60 C. The yield of N -[4-(Npentachlorophenyl N methyl amino)butyl]-N ,N -dimethyl-N(2',5-dimethyl-benzyl) ammonium chloride of melting point 183 C. amountsto 356.5 g. (93.5% of theory, referred to the diamine used).

EXAMPLE 5 Preparation of active compound IX 108 g. N-pentachlorophenyl-N ,N -dimethyl-ethylenediamine (0.321 mol), 100 ml.xylene, and 25 g. allyl chloride (0.326 mol) are mixed, kept at 60 C.for 1 hour and then heated to 100 C. in the course of 5 hours. Themixture is kept at 100 C. for 48 hours. The crystals are then separated,washed with light petrol and dried in a vacuum at 70 C. The yield of N-[2-(N -pentachlorophenyl-amino ethyl] -N ,N -dimethyl-N -allyl ammoniumchloride amounts to 95 g. (71.5% of theory, referred to the diamineused). When recrystallized from diethyl ketone/ethanol (8:1), thecompound has M.P. 175l8l C. Carbon: found 37.47%, calculated 37.81%;nitrogen: found 6.72%, calculated 6.78%.

EXAMPLE 6 Preparation of active compound XXIV 81.3 g. N-pentachlorophenyl-N ,N ,N -trimethyl-hexamethylene-diamine (0.2 mol),130 ml. anhydrous methyl ethyl ketone and 34.1 g. p-ethoxybenzylchloride (0.2 mol) are kept at about 78 C. for 20 hours; the liquidreaction mixture is then treated with 300 ml. cyclohexane and cooledwith stirring. The resultant crystals of the ammonium salt are separatedand washed with cyclohexane. The yield of N 6- N -pentachlorophenyl-N-methyl-amino) hexyl]-N ,N -dimethyl-N -(4' ethoxybenzyl) ammoniumchloride of MP. 72 C. amounts to 109 g. (94.5% of theory, referred tothe diamine used).

The N pentachlorophenyl N ,N ,N trimethyl-hexamethylene-diamine used asstarting material is not yet known. It is prepared by adding a solutionof 109.4 g. N- pentachlorophenyl-hexamethylene-diamine (0.3 mol) in 163ml. xylene in the course of 40 minutes to a mixture, kept at 8490 C., ofg. 98% formic acid (1.7 mol) and 94 g. of a 35% formaldehyde solution(1.1 mol), and keeping the mixture at C. for 5 hours. For working up,the reaction mixture is treated with 700 ml. water, the upper phasecontaining the xylene is separated, the aqueous phase is renderedstrongly alkaline and extracted with cyclohexane. The cyclohexane phaseyields g. crude N -pentachlorophenyl N ,N ,N trimethylhexamethylone-diamine from which 108.5 g. of the purified product ofboiling point C./ 0.02 mm. Hg can be obtained by distillation.

EXAMPLE 7 Preparation of active compound XXV 69 g. N -pentachlorophenylN ,N ,N trimethyl-hexamethylene-diamine (0.17 mol) dissolved in 100 ml.methyl-cyclohexane, are mixed with 39.8 g. 2,3-dibromoallyl chloride(0.17 mol) and heated at 80 C. for 18 hours. The reaction mixture isthen diluted with 400 ml. methyl-cyclohexane and allowed to cool. Thesolvent is decanted from the precipitated reaction product; this isstirred again with 200 ml. methyl-cyclohexane at about 80 C., and theammonium salt is separated from the solvent.

The ammonium salt is finally heated to 70 C. in a high vacuum. 95 g. ofa hygroscopic material, N -[6-(N-pentachlorophenyl Nmethyl-amino)hexyl]-N ,N -dimethyl- N -(2',3'-dibromoallyl) ammoniumchloride, are obtained. Bromine: found 24.8%, calculated 24.9%;chloride: found 32.7%, calculated 32.3%; nitrogen: found 4.43%,calculated 4.37%.

The 2,3-dibromoallyl chloride used as starting material can be obtainedby adding bromine at -10 C. onto propargyl chloride dissolved in carbontetrachloride; B.P. 63-68" C./8 mm. Hg.

EXAMPLE 8 Preparation of active compound XXVI 12 g. N -pentachlorophenylN ,N ,N triethyl hexamethylene-diamine dissolved in 90 ml. cyclohexaneare mixed with 4 g. methyl iodide and kept at 80 C. for 3 hours. Theprecipitated ammonium salt is separated and washed with cyclohexane.Yield 7 g. N -[6-(N -pentachlorophenyl N ethyl-amino)hexyl]-N ,N-diethyl-N methyl ammonium iodide. Carbon: found 39.0%, calculated38.6%; nitrogen: found 4.70%, calculated 4.74%; iodine: found 21.1%,calculated 21.5%.

The N -pentachlorophenyl-N ,N ,N -triethyl-hexamethylene diamine isobtained by heating hexachlorobenzene with an excess of NBN ,N-triethyl-hexamethylene-diamine at 225 C for hours, treating thereaction product with a sodium hydroxide solution and cyclohexane,distilling the components soluble in cyclohexane, and separating thefraction of RP. 164 C./ 0.009 mm. Hg.

EXAMPLE 9 Using the procedure of Example 4 with corresponding molaramounts of N -pentabromophenyl-N -iso-butyl- N ,N-diethyl-trimethylene-diamine and 3-bromobenzyl bromide, thecorresponding N -[3-(N -pentabromophenyl- N -iso-butyl-amino) propyl] -N,N -diethyl-N -(3 bromobenzyl) ammonium bromide is produced.

Advantageously, in accordance with the present invention, in theforegoing formulae:

A represents lower alkylene having at least 2 carbon atoms, such as di-,tri-, tetra-, penta-, and hexa-methylene, especially lower alkylenehaving 2-6 carbon atoms;

R represents hydrogen or alkyl having 1-4 carbon atoms, such as methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, especiallyalkyl having 1-2 carbon atoms;

Each R" respectively represents:

(a) Aryl-methyl having 61O carbon atoms in the aryl moiety, such asphenylmethyl (i.e. benzyl), naphthylmethyl, etc.; such aryl-methyl whichis substituted with one or more and preferably up to 5 to 7 of thefollowing substituents;

Halo, such as chloro, bromo, iodo and fluoro, epecially mono-, diandpolyas well as mixed diand poly- -chloro, -bromo, -iodo and -fiuoro,most especially chloro and bromo;

Nitro;

Lower alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy, sec.-butoxy, tert.-butoxy, especially alkoxy having l-2carbon atoms;

Alkyl having 1-12 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec.-butyl, tert.- butyl, amyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl;

Methylene dioxy;

And mixtures of such substituents;

(b) Or lower aliphatic, such as lower alkyl, i.e., methyl to tert.-butylinclusive as enumerated above under R, and the like; lower alkenyl,i.e., vinyl, w, B- and 'y- -allyl, butenyl; lower alkylnyl, i.e.,ethynyl, propynyl (e.g. propargyl), butynyl, and the like, especiallyaliphatic having l-4 carbon atoms, and more especially alkyl having 14carbon atoms, alkenyl having 2-4 carbon atoms, and alkynyl having 2-4carbon atoms;

(0) Or halo-lower aliphatic, such as the corresponding chloro, bromo,iodo and fluoro substituted lower aliphatic mentioned immediatelyhereinabove, and corresponding mixed chloro, bromo, iodo, fluorosubstituted lower aliphatic, especially such correspondinghalo-aliphatic which is chloro and/or bromo substituted, and mostespecially such halo-aliphatic having l-4 carbon atoms, and particularlyhalo-alkyl having 1-4 carbon atoms, halo-alkenyl having 2-4 carbonatoms, and halo-alkynyl having 24 carbon atoms, including mixed halosubstituents; with the proviso that at most only one R" radical isarylmethyl or substituted aryl methyl, the remaining radicals (2) or allof such radicals being otherwise lower aliphatic or halo-lower aliphaticas noted hereinabove;

Each X respectively represents chloro or bromo; and

Z represents a salt forming anion such as chlorine, bromine, iodine,fluorine, methyl sulfate, toluene sulfonate, dimethyl phosphate,dipropyl phosphonate, and the like, especially halogen and mostespecially chlorine, bromine and iodine, alkyl sulfate, and mostespecially lower alkyl sulfate, aryl sulfonate, especially benzenesulfonate and alkyl benzene sulfonate, and particularly lower alkylbenzene sulfonate, alkyl phosphate, especially lower alkyl phosphate,alkyl phosphonate, and especially lower alkyl phosphonate, and the like;the anion Z forming with the penta-halo-phenylamine ammonium cation, asalt which is soluble in water, preferably to give at least aconcentration of 0.01%, the chemical constitution of the anion beingotherwise of no particular importance, especially considering thebactericidal properties of the instant salts.

It will be realized by the artisan that 011 of the foregoing compoundscontemplated by the present invention possess the desired bactericidal,especially phytopathogenic bactericidal, activity, all of such compoundspossessing extremely low phytotoxicity as regards cultivated plants, aswell as extremely low toxicity towards warmblooded animals.

What is claimed is:

1. N-pentahalophenyl-amino ammonium salt having the formula:

in which A is lower alkylene having at least 2 carbon atoms, R isselected from the group consisting of hydrogen and alkyl having 14carbon atoms, each R respectively is selected from the group consistingof phenylmethyl and naphthylmethyl; substituted phenylmethyl which issubstituted with at least one member independently selected from thegroup consisting of halo, nitro, lower alkoxy, alkyl having l-12 carbonatoms and methylene dioxy; lower and halo-lower alkyl, alkenyl andalkynyl; with the proviso that at most one R" is selected from the groupconsisting of such phenylmethyl and naphthylmethyl and such substitutedphenylmethyl, X is selected from the group consisting of chloro andbromo, and Z is a halo anion.

2. Salt according to claim 1 wherein A is lower alkylene having 2-6carbon atoms, R is selected from the group consisting of hydrogen andalkyl having l-2 carbon atoms, each R" respectively is selected from thegroup consisting of phenyl methyl; naphthyl methyl; substituted phenylmethyl which is substituted with at least one member selected from thegroup consisting of chloro, bromo, nitro, alkoxy having 1-2 carbonatoms, alkyl having l-l2 carbon atoms, methylene dioxy, and mixturesthereof; alkyl having 1-4 carbon atoms; alkenyl having 2-4 carbon atoms;alkynyl having 2-4 carbon atoms; and such alkyl, alkenyl and alkynylwhich are substituted with at least one member selected from the groupconsisting of chloro and bromo;

13 with the proviso that at most one R" is selected from the groupconsisting of such phenylmethyl, such naphthylmethyl and suchsubstituted phenylmethyl, X is selected from the group consisting ofchloro and bromo, and Z is an anion selected from the group consistingof chloro, bromo and iodo.

3. Salt according to claim 1 wherein such salt is N[6-(N'-pentachloropheny1 N methyl-amino)hexy1]- N ,N ,N -trimethylammonium iodide.

4. Salt according to claim 1 wherein such salt is N [2 (Npentachlorophenyl-amino)ethyl]-N ,N -dimethyl-N -allyl ammoniumchloride.

5. Salt according to claim 1 wherein such salt is N-[6-(N-pentachl0rophenyl N methyl-amino)hexyl]- N ,N -dimethyl N (2,5dimethylbenzyl)ammonium chloride.

6. Salt according to claim 1 wherein such salt is N-[6-(N-pentachlorophenyl N methyl-amino)hexyl]- N LN -dimethyl-N (2,4dimethylbenzyl) ammonium chloride.

7. Salt according to claim 1 wherein such salt is N -[2 (N'pentachlorophenyl-amino)ethyl]-N ,N -dimethyl-N -(2,5-dimethylbenzyl)ammonium chloride.

References Cited UNITED STATES PATENTS 2,099,525 11/1937 Krzikalla et al26096 2,087,131 7/1937 Taub et al. 260567.6 2,918,401 12/1959 Copp260567.6 3,328,464 6/1967 Gundel 260567.6

LEON ZITVER, Primary Examiner M. W. GLYNN, Assistant Examiner US. Cl.X.R.

P UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,518,308 Dated June 30 1970 Invent r( Werner Daum and Hans ScheinpflugIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

001. 2 line 55 N -pentachlorophenyL-N ',N -dimethyl-ethylamine diamine;"ethylamine" should be -ethylene--.; 001.3, line 72 "malvacearm" shouldbe -malvacearum--; Col. 4, line at the end of the formula outside theclosing Bracket, "C'l" should Be --Cl Col. 4, line 9 "N -[2'-" should be-N -[2- l 1 1H Col. 4, line 15 Cl N "CH should be --H-.;

C01. 4, line 33 at the end of the formula outside the closing bracket"01+" should be --Cl' Col. 5, line 59 "dially" should be --dial1yl-;

Col. ,6, line 2 butyl] should be butyl Col. 6, line 22 "chlorallyl"should be --chloroa1ly1--; Col. 6, line 50 at the end of the formula,outside the closing bracket "01-" should be c1 Col. 6, line 62 at theend of the formula inside the closing bracket, "00 11 should be --0C HCol. 7, line in the formula CH should be "5 Col. 7, line 17 -""forma%ins" should be --formulations--; Col. .7, line 44 "slice". should be"silica"; Col. 7, line 52 "espectially" should be --especially--; Col.8, line 8 after "of" insert --the--. Col. 8, line 14 baeteriacidally'should be --bacterieida1ly--; Col. 8, line 15 "pothogenically" should be--pathogenically--; Col. 8, line' 19 insert a comma after "spraying";Col. 8, line 36 "dresing" should be --dressing--; LCol. 8, line 42"limitating" should be "limitationl C01. 94, line 72 "210" should be--2o1--; I Col. 11, line 71 "alkylnyl" should be --alkynyl-; Col. 12,line 32 "011" should be --all--.

Signed and sealed this th da f 0 (SEAL Y 0 ctober 197i).

Attest:

ELJIQIARD MILETCHELJR. WILLIAM E. SCHUYLER, JR.

estlng OfflCer C i ioner of Patents

